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We report marine dissolved organic carbon (DOC) concentrations, and DOC Δ¹⁴C and δ¹³C in seawater collected from the West Indian Ocean during the GO‐SHIP I07N cruise in 2018. We find bomb¹⁴C in DOC from the upper 1,000 m of the water column. There is no significant change in ∆¹⁴C of DOC in deep water northward, unlike that of dissolved inorganic carbon (DIC), suggesting that transport of deep water northward is not controlling the¹⁴C age of DOC. Variability of DOC ∆¹⁴C, including high values in the deep waters, is more pronounced than in other oceans, suggesting that dissolution of surface derived particulate organic carbon is a source of modern carbon to deep DOC in the West Indian Ocean. Low δ¹³C are present at two of the five stations studied, suggesting a source of low δ¹³C DOC, or additional microbial utilization of deep DOC.

 

The >5,000‐year radiocarbon age (¹⁴C‐age) of much of the 630 ± 30 Pg C oceanic dissolved organic carbon (DOC) reservoir remains an enigma in the marine carbon cycle. The fact that DOC is significantly older than dissolved inorganic carbon at every depth in the ocean forms the basis of our current framing of the marine DOC cycle, where some component persists over multiple cycles of ocean mixing. As a result,¹⁴C‐depleted, aged DOC is hypothesized to be present as a uniform reservoir with a constant¹⁴C signature and concentration throughout the water column. However, key requirements of this model, including direct observations of DOC with similar¹⁴C signatures in the surface and deep ocean, have never been met. Despite decades of research, the distribution of Δ¹⁴C values in marine DOC remains a mystery. Here, we applied a thermal fractionation method to compare operationally defined refractory DOC (RDOC) from different depths in the North Pacific Ocean. We found that RDOC shares chemical characteristics (as recorded by OC bond strength) throughout the water column but does not share the same¹⁴C signature. Our results support one part of the current paradigm—that RDOC is comprised of structurally related components throughout the ocean that form a “background” reservoir. However, in contrast to the current paradigm, our results are consistent with a vertical concentration gradient and a vertical and inter‐ocean Δ¹⁴C gradient for RDOC. The observed Δ¹⁴C gradient is compatible with the potential addition of pre‐aged DOC to the upper ocean.

 

ABSTRACT This study describes a procedural blank assessment of the ultraviolet photochemical oxidation (UV oxidation) method that is used to measure carbon isotopes of dissolved organic carbon (DOC) at the National Ocean Sciences Accelerator Mass Spectrometry Facility (NOSAMS). A retrospective compilation of Fm and δ 13 C results for secondary standards (OX-II, glycine) between 2009 and 2018 indicated that a revised blank correction was required to bring results in line with accepted values. The application of a best-fit mass-balance correction yielded a procedural blank of 22.0 ± 6.0 µg C with Fm of 0.30 ± 0.20 and δ 13 C of –32.0 ± 3.0‰ for this period, which was notably higher and more variable than previously reported. Changes to the procedure, specifically elimination of higher organic carbon reagents and improved sample and reactor handling, reduced the blank to 11.0 ± 2.75 µg C, with Fm of 0.14 ± 0.10 and δ 13 C of –31.0 ± 5.5‰. A thorough determination of the entire sample processing blank is required to ensure accurate isotopic compositions of seawater DOC using the UV oxidation method. Additional efforts are needed to further reduce the procedural blank so that smaller DOC samples can be analyzed, and to increase sample throughput. 

ABSTRACT In practice, obtaining radiocarbon ( 14 C) composition of organic matter (OM) in sediments requires first removing inorganic carbon (IC) by acid-treatment. Two common treatments are acid rinsing and fumigation. Resulting 14 C content obtained by different methods can differ, but underlying causes of these differences remain elusive. To assess the influence of different acid-treatments on 14 C content of sedimentary OM, we examine the variability in 14 C content for a range of marine and river sediments. By comparing results for unacidified and acidified sediments [HCl rinsing (Rinse HCl ) and HCl fumigation (Fume HCl )], we demonstrate that the two acid-treatments can affect 14 C content differentially. Our findings suggest that, for low-carbonate samples, Rinse HCl affects the Fm values due to loss of young labile organic carbon (OC). Fume HCl makes the Fm values for labile OC decrease, leaving the residual OC older. High-carbonate samples can lose relatively old organic components during Rinse HCl , causing the Fm values of remaining OC to increase. Fume HCl can remove thermally labile, usually young, OC and reduce the Fm values. We suggest three factors should be taken into account when using acid to remove carbonate from sediments: IC abundance, proportions of labile and refractory OC, and environmental matrix.